Method for recovery of vanadiumfree chromate and aluminate



P 1952 T. s. PERRIN ET AL METHOD FOR RECOVERY OF VANADIUM-FREE CHROMATE AND ALUMINATE 2 SHEETS-SHEET 1 Filed Nov. 15, 1948 FIG. I

"M90 (DOLOMITIC LIME) TO 10 VBAUME CdNCENTRA FILTER 2 CRYSTALLIZER ALUMI NA HYDRA TOM s. PERRIN ZI ROBERT a BAN ER Sept. 1952 I T. s. PERRIN ET AL 2,612,435

METHOD FOR RECOVERY OF VANADIUMFREE CHROMATE AND ALUMINATE Filed NOV. 15, 1948 2 SHEETS-SHEET 2 FIG 11 FROM FILTER l RAW PH I l l2.5 LI%uoR PbSO4 RETURN T T LIQUOR? To H 85-9 PPT OF ALUMINA Ifi'z ifi FILTER HYDRATE u QUOR FILTER CAKE CAKE Pb CY 04 Pb s )2 To CHROMATE REoovERY FILTER l: l.

2 25 8433 NcIOH To DEISSOLVE (IMPURE) CONC. SOLN. CAK

" 2 5 0R TOREDUCE cvo H2 5 AND PPT PbS To DILu TE W SOLN I.I FILTERZ3 H FILTER cAKE*2 um 0 Pb s, Cv oI-I) so N. com a v IEL- FILTE FILTER CAKE FILTER FILTE Pb 50 CA '4 I PURIFIED I- V NaAl 0 SOLN. OF! I BEL-v l Cvz 4} 3 COMPLEX TOM s. PERRIN ZI ROBERT G. BANNER @MZM Patented Sept. 30, 1952 FREE GHROMATE AND'ALUMINATE .Tomrs. Berrin-t-andkobert G. Banner,gPainesville,-.--

Ohio; aassignors to .Diamond Alkali Company, Cleveland,- Ohimacorporation of Delaware.

Application November- 13, 194s;=seria1:ivo.s9;9s4i w v 7 Claims. -1

Thlsinvention relatesato a'imethod I0r:1:ecoyer-= ing:,vanadium and :aluminum =.values;from solutes comprising the same, sand; more -..particularly re-. lates to .a:-methodv iorithexrecovery:ofgvanadiumand aluminum :values .-.from solutes:containingra: relative prepondeiance- :of chromiumzvalues; and. lesser amountsaotcaluminum and zvanadium :vale-z ues, in whichcmethodr-wvanadium:sequestering/ agent is:remployecliami ist-recovered;dire.ctly:;and.. recycledllin u'the :prqcess; in dtheyiormr. recovered The method also'providesior; obtaining. solutions of. :aluminum hzsalts. iand'a'chromium :sa-lts rsuba stantially iuncontaminated by vanadium; "salts and by each other. The method has particular. applicability; :to- .zthernlkaline:r-liquors; :obtained from-sieachingzof, alkalirchrome (OIBIIOEJStSS;

v It. has;:heretdforembeemsproposedcnto recover: vanadium values:generallyiassociated withoaqea ueonsziliquonsr; containing. chromatersalts. :ssuch',;. i'ormxamplegas the -;-auueousi leach-x:liquors,;ob-..z-

tained from:thezialkalieroastinezoi' chromite zoresrz' Speeifically,:;.:it 1185;: been r.-proposedw.-to;;-recoyer;- vanadiumiizaluessfromusuch 'liquors .by atmethod whichcconsists essentially. in; acidifyinggihezzaqueousrleachcliquors. rwithzisulfuricz acid; to 2 about 1313214361,:togformi'blchromate; ifractional-lyaerystallizinaialkali-:metalssulfateiromjthe; liquors; filter;-, ins:itheuycrystallizedrzalkali :1metal-;;sulf.ate;.-;con-\:

centrating. .;the. i'flltziatei and .crystallizin alkali. metal bichromate: 2.- :The:alkali.-metaltbichromates-i.

is separated-item the. mothervliquomfor exampleti. byzcentri-iuginau and. finallyi the -pH;.of the; mother. liquonds adjusted. etc i about r1.7,. .whereby;:.vanae:z diumiis;.preci-pitated andzrecoyered-as vanadium;

oxide; org-a hydrate uthereci: 'I'his -pmcessahas 1;:

of gthe. iflltrate .fromr-this precipitation; which is necessary:;-\for; high zyieldso! chromium\-yalues,.

results.' 'in .--.return :of the remainingmvanadiumx. which ,thusrrbuilds :up in concentration in n-the. recoverygsystem. Y

. Also: it has.- heretofore tbeerr proposed to -sp-s;

arate vanadium salts 0ccurring;.-.-in-=-solutionssof chromatesalts' by .=converting=the-vanadium salts.

to; ammonium metayanadaterand .precipitatingua barium;.-salteoi metavanadic;acid-:from slislrtlyt ammomacal: dilute aqueous..tsolutionsmcontaining. r therammoniunnmetavanadate;*which procedure;

is disadvantageous ra's incomplete. separation experienced due to relative.insolubilitwof barf-i I ium: ehromate in. ammoniacal. solutions, zoo-pres; cipitation" of remaining iron: and aluminum n;

thepsolutionsfurther. contaminates the: barium.

metavanadate, and: the; extraneous ammonium ion must subsequently be removed vfrom the main. chromium liquors, wherebyan extra steps added to thezchrome recovery prooessi...- 1

It has also been proposed -to vpiecipitate a 1 cium. salt of vanadic acid-from slightly z-acidselutions containingvanadioions, the @aoid; being.

employed ..to ..prevent.- the r precipitation. .of t ironor ,aluminumhydroxides. The ;.oalcium preclpav itate. is thereafter processed. to; recoverthe yan adium in the. desiredformi .-This metho d, I how-- everefficient it may be for recoveryof vanad: values, is precluded by .the .solubilityofcalc;.- ohromate in acid solutions where. .-.chromee recovery is important, since calcium. chromate.oo-.. curs as av contaminant-0f sodium. bichromateQin the ultimate \bichromaterecovery, f f Moreover, it has heretofore been propose dlto hold back vanadium-salts iromaqueousjsblu tions obtained-after the alkali roasting .of. ehro.-=. mite. ores, by. incorporating alkaline ,.earth-,.metal oxides lwith'such ores, prior tovtheroastingQ ...,The. alkaline earth metal oxides...in .thelroastn form vanadate salts' which are relatively-insole uble .in water and arev thus. to some extentfheld;

back and not carried over into the chromate,

process. liquors, when .the..roastvis leached with water. In addition to the disadvantage" thatv vanadiumis only partiallyjhel'd back .by'..]suchj treatment, and thus appreciable. amounts -oi v vanadium. in .soluble iform.-. are. leached, outwith.

the chromium .values a furtheruefiec'tof process is that the vanadium held. back the' leached residue from the roast. mixjis there after unavailable for.;recovery. by. economically; satisfactory methods,.'due to the large ;bulli, ..'6ii. material which must be processed to .rec'oyl'er the relatively small amount of-vanadiumfpresentl therein; As to the aluminum values generally associated with chromeores;from which the chromium": and-vanadium values are sought. to be recovered; I it has heretofore-been. the 'practice'iinjithe' art to precipitate alumina hydrate, contaminated) .with. chromium values prior tojthel precipitation. of the. chromium and vanadium vvalues and to discard. the impure alumina or. "to

theproduction of low-grade. aluminum.

ica1s,.such as impure "alum; This procedur hast involved a-loss of alumina, the ;va-lue.. pigm nt contaminating the' alumina.

In contrast to these prior art proposals, the

I present inventionpresents an efficient method for the co -precipitation of Compounds of vanadium andaluminuim'fand for the recovery of purified solutions of chromium salts. Moreover, the

present method substantially precludes the accumulation of deleterious amounts of vanadium compounds within the chromate recovery system,

while simultaneously providing a cyclic process in which the vanadium sequestering agent is recovered and reused substantially without loss thereof. H

An additional advantage of the present invention over prior art practice isthat substantially pure alumina hydrate uncontaminated by chromium salts is recoverabletherefrom and is available as'a source material for a wide variety of aluminum-chemicals, for which it'could not heretofore beused in view of chromate contamina tion; Moreover. the expense of processing to obtain high-grade alumina is not significantly greater thanfthe expense of obtaining impure was -onl'y'of border-line utility.-

, noted-above} the present invention maybe applied to -a conyentional chrome ore treating process-with the adyantage that early in that process, the vanadium concentration is reduced to atolerable limit, "whereby its presence may be disregarded in the remainder of the chrome treatings'teps-especialIy since build-up of vanadium edespecia lly wherefound in ores predominating he h l pr w "These and other advantages of the invention appear more fully hereinafter from a general description' and-a specific example, both of which further elucidatethe manner in which the in containing sodium chromate, sodium vanadate, sodium aluminate, and other salts, and an insoluble residue are obtained. The liquor and residue may be separated by filtration, as at filter #l. The residue is dried and combined with further amounts of sodium carbonate (this time without the addition of lime), as" indicated byfthej' dotted line to the left of the mainstream of Fig; I, and separately recycled in the roasting and leaching process hereinabove described, with the result that further amounts of the chrome value contained'in the, roast residue are thereby removed. The leach liquor from the first roast and the liqnor from the recycle roast are combined and are designated in Fig; I as raw liquor, and as shown, ordinarily have a pH Within the range of l1-12.5.

mThe fraw liquor is treated with sulfuric acid alumina hydrate experienced by the prior art. Accordingly, a substantial advantage is gained in that a; further by-pro'diict of value is recovered from the chrome processing, which heretofore,

vention nay be pra ctice'd. Theinvention is more part cm ny described in connection with the drawings" forming. apartof the specification, in

ingi'an alkali roast method of treating chrome ores to recover chrome values therefrom, and,

'FigLTIIisa chemical process flow-sheet of the the process of Fig.1 immediately prior to the neutra ization'of. raw liquon v I rring now to Fig." I, the chrome bearing MgOl. One purpose of the sodium carbon- ;thereof; The lime. is. employed primarily toimainta i'n, a granular consistency in th roast mix'fdu'r the roasting process, which may suit- I, bl' minish'the' amount of I water 'extractable vanaarried outin a rotary kiln or other cona'sting'r'n'eans, and secondarily, to didiu'mjsalts formed during the roasting of the: ore. The roasting of-the-mix is carried out at a temperrisk a chemical process flow-sheet illustrat- '55 method of the" present" invention interposed in" atur'e ranging between'ZOQO" and 2200 F., after 7 which thefr oa'st 'is'co'oled and leached with water. Asfaie'siilt of theleaching-step, an aqueousliquor- (78%), or with acidic solutions recovered subsequently in the process, to bring the pH of the raw liquor within the lrange 8.5-9 in order to precipitate-the aluminahydrate, which maybe present in the ore in an'amountas high as 15%.

The alumina hydrate, contaminated with'appre-' ciable amounts of chromium as chromates, is sepwanted from the aqueous partially neutralized liquors by filtration, as at filter #2, the filtratethen being referred to as neutral. liquor. Th precipitate carries with it approximately of the.

original vanadiumv values occurring in the fraw liquor, the remainder being carried into the neutral liquor assolubie vanadates. It. is this,

precipitate 'which inprior art practice hasgbeen 1 discarded or sold as'low-grade, impure alumina hydrate.

The neutral liquor! is next acidified with Sui... furic acid (78%) to bring the: pH of the solu-i tion to about 4.4, whereupon chromato ionis converted to bichromate ion in-the solution.

Thereafter the solution may be suitably-concentrated, preferably to about 60 B.,' -and then cooled to approximatelyroom temperature. The

concentration and' cooling steps resultinl'the crystallization of sodium "sulfate, at crystallizer #L-the motherliquor comprising the chromate values as bich'rornates and'the vanadium values as an acid or acid'salt' thereof; The crystallized sodium sulfate is removed from the mother liquor by centrifuging as at centrifuge #L Theacid mother li'quor',* after the removal "of sodiuin sulfate, is referred to as redliquor.

However, aspo'intedout more fully below; re-5 turn liquor usually-is employed and in su'chca'se' the crystals are' c ntam'inatedwith vanadium-toan extent of between-0.-2 and"1% taken as so-' dium vanadate. This amount of vanadium sufilcient tocause-substantial difficulty in tan ning operations and to detract seriously from" the value of the bichroma'te" as'a raw material for chromate pigments." V

The return liquor carries with it appreciable The red: liquor is further concentrated in order to crystallize the-bich'romate "values therefrom; After suit-.

. able concentration, for examplef-to' 'lo" B., so='- dium bichromate crystalliz esfrom the'concen trated red liquor atcrystalliz'er #2 and'is centrifugedatcentrifuge #I-to remove the mother liquor, which liquor is" designated as return liquor.The crystals are thefinishedproduct of the-process" and are, if no return 1iquor -=has" been used inmake up'of the red liquor, reason-'* ably free ':of 'vanadiumQand other impurities."

dotted 11115 to the might lot *the' imainss'tream of Fig; I; as apart'or the acizit-required toneutralizev raw; liquor-3' Y It will be appreciated. that such recycling or the -return liquor" ultimately results in accumulating an undesirable. amountof vanadium salts within- :the system, which saltscontaminate :the -bichroma'te crystals' obtained thereirom'" and r adversely affect the crystallization of blchromatea as'well 'as the-:chemical-and physical-properties:oi the chemicals subsequently tob'e obtained trom sueh bicliroma'tes. .anoweverp discarding the retum liquor is hot 'a 'solutiona. to the l proble'm 'aseconomically wasterulvquanti ties oi bichromates wouldbe lost-. Heretoiore, various of the prior art expedients set forth above for avoiding vanadium buildup and excessive concentrations'pf vanadium finished b'ichromate have been resorted to with little success.

Elia-accumulation. of undesirable. amount .oi vanadium compounds. .111 recycled chromate liquors .is substantially precluded by the. method or the. present invention-in that the vanadium concentration is reduced-to a tolerable limit in the .rawliquor? stage or chromium recovery, .and even the remaining smallxamount .oi-vanadium is disenabled. to buildup-in the system, since-recycled liquors .are also. subjected .to treatment. Accordingly, better crystal .iormand a more rapid crystallization of a .purer bichromate .is obtained with the further advantage that vanadium and aluminum-compounds in commerciallya cceptar ble .iorms are "recoverable... A method ior. the separation of vanadium and chromium values by treating solutescomprising the sam'e'with lea-d ions to obtain a precipitate of lead vanadate does' not form a part. of the .presentinvention, except. as .herein claimed, but. is, disclosed: and claimed ;.in .a co-pending,application, :S er. .No. 59,935, filed of even date-herewith, in the name of oneof the present inventors'and another, new PatentNol 2,583,591,.datedJanuary .29., 1952.

The present .invention is. directed to a method 01. removing vanadium and aluminumlsalts .Irom.

- Fig.1..

solutes containing a preponderance oi-a mixture of. alkali metal chromates with alkali metal aluminates, and a. minor proportion of alkali metal vanadatea-which includes the steps. 01. providing a source oi lead ions .in a solutioncomprising tion to a. pH with-in,th e range of 8-9, therebylto I said-solutes, adjusting the alkalinity oi said=solu.-.

.55 coeprepipitate. substantially. all .01 the vanadate lons'.-;and-.a minor proportion of the chromate ionsmoi-said solutes. as their .lead- -saltsn and to convert allot said-. alkali metal. aluminates to H aluinma hydrate and separating the :co precipiinvention also includes. :the...recov.ery= of lead, vanadium, chromium and aluminumvaluesfrom said co -.precipitate in accordance with steps to beset forth more fullyhereinaiter.

. tate-irom -.the remainder. of said solution. The

Reierenceis made to. Fig. .11 .of the draw n whereinthe present invention is shown interposed in:;an. alkali-..roast process for the recovery of bio; .omates from chromium: bearing-ores, .such

as thatfi'llustrated. by theprocess .ofFig; I. The

invention is not tobe limited however, to -use in, .conjunctionwith the-process of Fig.1, as it isapplicableto any. l quors containing chromium. r

and .:;vanadium values and -.:having soluble: alumi;-;

nate .:compounds .therein lwhichmsually :;requires; .75v

therexi'stence oi a rpHa'sumientlyralkallmetcnper a. mi't the existence: oi suchialuminatesun .therisyl tem in soluble form, such-ras a pH- 01 2104241 For convenience, *howeverpthe inventiorriisrdeseribed in connection "withlthe-process oi 'Fig 'L 2- a e A suitable lead compound such as leadrmdde',; lead-hydroxidalead sulfate',. or basic leadsulfata: is made up into an aqueous slurry andi'radded tothe J raw liquor" with agitation; .Ima'ddition tom the dead compounds-already noted,-which-=oom-:: pounds are recognizedin the 'art' as 1rel'ati-velye water insoluble, soluble: lead salts,rsuch aslleadu nitrate; lead chloride, 'or lead acetate, may also be usedin the practice-of the present -inventionw where the vanions of suolr oompoundssare not-ob jectionable :contaminants :o'f-x the chromatealiquorsr: subsequently tob'e obtained. In general it'is, pr ier'redrin the practiceof the-"present= inventionito 1 employ leadsulfate at this point oi -the proce's's especially:since' the lead sal t may; if 'desir edi be recoveredas lead sulfate-and:maybe' recyoled for-' re-use; The addition of a such suitable lead-some r: pound to the 'raw liquor"* efiects the removal if substantially: an. of the vanadium I ions': -and -a minor proportion-of the: chromate ions asp-re ci'pitates comprising 1 "their 1 lead salts Either:-

The .filter cake, as 'obtained-Irom 'the above series: of steps, may be discarded ifdesired, al though 1 economic advantages otherwise --'ob tainable in accordance with' 1 one. procedure- 0f the presentinvention' are thereby lost. Therefore,-- when considering the method of thew-present m-=- vention relative to commercial alkali roast"pro:.;.- cessesfor the recovery of chromium'from 'its oresj it is. preferable to provide for the recovery of at least the lead valuesifrom.the fiIter-cakeJi .QJ

Suchrrecovery' may suitably be accomplished by 11 either: of two routes, the first of which is illustrated in Fig. II by the dotted'flow line to the-left of themairrstream- .followingl. filter cakeand comprises" essentially. the 'recovery of the "leadvaluesas substantially water'in'soluble leadsalts :other .than lead 'chrom'ate .or. lead vanada te; for

' example, lead sulfate- .111 following: this 'firs't route, the .filtertcakeis contacted withan 'acid suchias aqueous sulfuricacid, to convert the lea chromate and lead vanad'ateitherein 'to the corre' sponding lead salts,1theraluminumychromiu and vanadium values .of the filter cake-being thereby converted to water soluble "cornpoun a l from which insoluble lead sulfate isreadily sepa rated, .forsexample, by-filtration of the aqueou's :acid solution obtained. by so treating '.:theifilter:-' cake. Lead sulfatev thus obtained. may be fire-" cycled preferably. as such toiurther raw:li'quor to aid in .the separation. of furtheriivanadiuma therefrom; The aqueous. "aluminum :sulfate solutioncon taining relativelysrnall amounts: :of 'chrom'ium and vanadium compounds. mayv beflusedifind'u'sa.

where;relatively.=small amounts ot chromium and wanadium:compoundssthereinzdo not'rdeleteriousw 'sources,;such asbarium sulfate or barium hyamass-a:

.pByi the. second route, {the chromium, vana diurn and aluminum values may-be recovered'separate- 1y, lead being recovered as lead sulfate and recycled .to'the' raw liquor as'in the first route.

The ,second routeis illustrated by that portion of Fig. ,lli-whichfollows =filterhcake l., The filter cake comprising the co-precipitate of lead chromate,' lead vanadate, and alumina hydrate ,is

The caustic sodaliquorispreferably heatedanda agitated and the filtercake added thereto during such'agitation, in order to efiect'efficient and sub: stantially complete, solution of the ingredients of the ,fi -lter cake. After solution of the filter cake. hasbeen completed-a suitable source of sulfide 'ion is introduced into the solution to reduce the chromateionsto chromicions and co-precipitate lead sulfidewith chromic hydroxide. 5-

Thesulfideion may be Supplied from any suit-' able source, such,.for example, as hydrogen sulfide; sodium sulfide, otheralkali metal sulfide, or

alkaline earth metal sulfide, such as the sulfides of barium and calcium. Whensubstantiallyall The co-precipitate of lead sulfide and chromicf hydroxide iSf separated from the mother liquor suitably at filter 3.,

,The corprecipitate is preferably recovered for further processing in accordance herewith, particularly to recover the lead values therefrom for further use in sequestering vanadium ions from additionalquantities of raw liquor The fil trate comprising aqueous sodium aluminate, to gether with; soluble vanadate salts, may be furtherpurifi ed by treating it with a suitable source of barium ions to precipitate the vanadate ions therefromjand leavethe sodium aluminate solu- 1 tionsubstantially uncontaminated. The. barium" ions may be supplied from soluble barium salts; suchas the barium halidesv or from less soluble droxide. The amount of barium compound added to the, solution of sodium aluminate. is suitably within the range of 5-10 mole of the barium compound per-mol of, vanadate ion calculated as sodium ,metavanadate. The precipitate which forms'and is separated by filtration appears to be agbarium-vanadium complex and is presently of unidentifiedcornposition;:. The mother liquor contains the aluminum values from thechrome ore as sodium aluminate substantially uncontaminated by foreign substances other than sodium to 'chromic sulfate. The lead sulfate is" recycle droxide; theafilter ,cake, 2, from; filtenfipis suitably; treatedzrwithl an: acid;. such-.1125. sulfu ic acid; dissolve their chromic; hydr ide and, dec mn s the lead sulfideito hydrogen sulfideand'leadi-sule fate; Hydrogensulfide 'IeQONQZQG-JMJ this point may-ibewrecyclediin the process-for reduction oijj chromate; ion ,Though any suitable acid may be used-,atcthis' step,t.aqueous sulfuric acidispreferred as .lead,.in' the form o'flead sulfate, :is ob,- a

tained as a precipitate and maysuitably be re-,

coveredbyfiltration andrecycled as shown, and, soluble. chromic sulfate is;;obtained in: aqueous acidisolution; from 11-W 1Ch..-. may... r ad ly b recoverediaitertm lead separations :In order that those skilled inztheart maybctter, understand thedetails; of the method iof; the; present; invention and-.a preferred manner inwhichgthesame may; be carried into effect, the followingspecific, example is offered: .i; liemocctoj. vanadium and aluminum H Two liters offraw liquor containi ng 0388*g1 p. -1.-- oivanadium calculated as sodium-metavanadate. 49.7 g. 1531'. of alur'n'inunioXide'asifliOa and g. p l-of chromium calculated as sodium chromatedihydrate aremiXed with 24.6 gramsof lead -'sulfate, which has been s'lurried with water; to form'athick panache ratio-of lead sulfate to sodium mtavanadate being 14:11. l-lo millili'ters' of sulfuric acid (78 are slowly addedjto -the mixture of raw liquor and lead sulfate over-a period of 1 /2 hours with vig'orous;agitation.-- The precipitate is separated from 'thef'solutionby filtration. An analysis of the filtrate showstliatf' 92.4%; of the vanadium originally contained in the raw liquor is removed in the precipitate.

Recovery of aluminum, chromium, vanadium n l a 1 I .The precipitate is added slowly with-agitation to-136 milli'litersof 47.9% aqueoussodium hydroxide (5 excess over the amount required toreact with-the aluminum andleadcompou'ndsin the precipitate). Theaquecu'ssodiu'm hydroxide; is suitably added at atemperaturevery nearits boiling point; After the solution oftheprecipi tate has'be'en comp1eted,28 grams of 'sodiumsul fide monohydrate are added toflthe solution precipitate-the lead therein as lead sulfide; rep-" du'ce the chromate ions and "co-precipitate" chroniic" hydroxide therewith. Thefamount" or sodium sulfide'to; be added-"to the solutionds readily calculated from the amt'unetr leadsul fate added tothe raw liquor" and-from an analysis of the co-precipitate-ior"chromate id The solution is-then diluted witli anequaivmm of water and agitated-vigorouslyyfor several-min utes and the precipitate snowed" to settle. co-pre'cipitate' of lead sulfide'--andchror'ni droxide 'i's separated 'from' -the' vanadium o taining sodiuni'faluminate "solution b'y-fil' atio A determination-of the amount of variadium' con tained in the filtrate" shows that 94 *of that i removed from the raw liquor remains'in filtrate. The co-precipitate 'ofQIeadsuIfid chromi'c'hydroxide is treated with 35 millilit' so 78% sulfuric acid in order-to converthe sulfide to leadisulfate' and the chromic-hydrox de toadditional quantitiesof ra liquor i for ur thei recovery or the vanadium saus 'thcreiri; as

hereinabove indicated, and the. hydroge'n 'sulfide" J 5539 rotsodiumsulfiderto reduce ;,thezchromatezion;and sprecipitate lead; isulfide. asci iereinabove; :noted. :JIEhe solution of; achromicz-sulfate is j.concentrated cand'd-Z :grams ofi;crystalline ichromicysulfate :iso- 1ateditherefrom.; Anaqueous solutionof: barium chloride :containing 23.2.6 :g'rams ofizzbarium, chlo- ':.'ride :isradded to" the sodium. aluminatelsolution'in border to precipitate the vanadate'ionsctherefrom, -the ,amount: ofxfiharium chloride addedthereto -bcing; inith'e ratio'gof '10-mols of barium chloride -:-p'er,imol of :vanadate calculated as sodium. meta- ;tvanadateicontained.in the: sodium .aluminate sorzlution. A barium-vanadium complex aprecipi- :atateaforms in:the solution, whichcprecipitatesconstains isubstantiallyiliall .of. "the vanadium present in thea sodium aaluminate solution:- ('about :1'.62 grams), as well; asrsubst'antia'llyalltof 'the b'arium frwhichwas .Jadded thereto in the form f 3 barium chloride. This condition is evidence'dby chemical :analyses of cthe" sodium :aluminate xis'olut'ion for 'rvanadiu'rn-iand bariumr The: precipitate is al- --lowed to settle and is finally separated from the 5sodium-aluminate solution by filtration. "Analysis of the precipitate shows that 945% of themlnadium retained" in the sodium aluminate solucipitate. anda substantiallyiyanadium and alum-is vanadium and alum'inumrsalt's:fromisolutes containing. 'a: preponderance, era 1 mixture' 'of Talk-all metal Y chr'omate'sl with :.-alkali: metalealuminates and a rninorproportion ofzalkalii metalivanadates, which includes..the-Z:-steps 'of xprovidinga source "of "lead ions "in: at-solution; comprising.='.said

jsolutes, adjusting the-alkalinity of said solution to aLpHvvithin the range of-8e9 to co precipitate tion is recovered by precipitation with barium L ion, which represents about 88% recovery of vanadium":based on theamount originally contained in the fraw--;,liquor.

While there have bee described various embodi-n'ients'fi-of the invention, -the*methods described are not intended to "be understood as limiting theifscoipei'of theiinilention as it is realizedthat changes therewithin are possiblev and it is further intended that ichelement: recited in any oil. the following claims is to be: understood sis-referring to all i'e'quivalent elements for accomplishing substantially the same results in substantially. the same orequivalent manner,; it being intended to cover the invention broadly in whatever form its principle may be utilized. --What,is,claimedis,:' ii; I

1-1;. The (method. of; i em vingizaandurecoverin vanadium "and; aluminum values ,from an alkaline solutionihavingfapI-I'of'atileast 10 comprising tially all of the vanadate ions and a'minor proall of said aluminum values to alumina hydrate,

and co-precipitate said alumina hydrate with said lead salts, and separately recovering the substantially vanadium and aluminum-free chromate solution and said co-precipitate.

2. The method of removing and recovering vanadium and aluminum values from an alkaline solution having a pH of at least 10 comprising the same as vanadates and aluminates and a preponderance of alkali metal chromates, which includes the steps of contacting such solution with a substantially water insoluble lead compound which provides a source of lead ions in said solution, to co-precipitate substantially all of the vanadate ions and a minor proportion of the chromate ions as their lead salts, adjusting the alkalinity of said solution to 'a pH within the range of 8-9 to convert substantially all of said aluminum values to alumina hydrate, and co-precipitate said alumina hydrate with said lead salts, and separately recovering the co-presaid solution of saidsolutes assaiwsour vanadium and aluminum 'values-from=a sol soluble barium and vanadiu 5. The -method* of-*-'removin substantially all ofth'e.vanadateions and a minor proportion toi". the; chromate ions of: s'aid s'olutes as" their 1 lead I salts and to 5 convert substantially all of the alkali, metal aluminates er said-solutes to alumina hydrate, sepa'rating-ithe co-precipi-tate vfrom the remainder ofsaid solution;-icontacting said co precipitate with aqueoussuli'urio acid-to convert said lead 'saltsto insolubleileadsulfate said insoluble leadl's'ulfate from said acid solution, and recycling said: insoluble lead sulfate to lea'dions. I i

4." The method of -removing andrecov'erin'g comprising the-sameas vanadatesand aluminates and "a preponderance of alkali r iietal ch mates,

which includes the-steps of contactin semisolution at pH 8-9 with-*aleadcornpound which provides a source'of" lead ons therein} separately, recovering the ';precipitate whichforins; con 'c't mg said s e i e W faqueous? alkali-a w hydroxide to-dissolv'e t fi a r lution, contacting" said- 1 mm; with Sum r fi ethe'chromate-ions to-the h sulfide" Separating sa d prec p tates -frq th Yr mainingsolution gontactilnglasaivd, Solutiq a Spur mi n -iprecipitatefe tate and saidsolution;

ciliitate; and .separat e recovering vanadium and aluminum salts from a solution comprising a preponderance of a mixture of alkali metal chromates with alkali metal aluminates and a minor proportion of alkali metal vanadates, which includes the steps of adding an inorganic lead compound to'a first aqueous solution of said solutes to provide a source of lead ions therein, adjusting the alkalinity of said first solution to a pH within the range of 8-9 to form a first co-precipitate including substantially all of said alkali metal aluminates as alumina hydrate, separating said first co-precipitate from the remainder of said solution, contacting said first co-precipitate with aqueous alkali metal hydroxide in stoichiometric excess of the amount required to react with the aluminum and lead compounds of said co-precipitate, to form a second solution comprising alkali metal salts of the elements of said first co-precipitate, contacting said second solution with a source of sulfide ions to reduce the chromate ions and to form a second co-precipitate of lead sulfide and chromic hydroxide, separating said second coprecipitate from the remainder of said second solution, contacting said remainder of said second solution with a source of barium ions to precipitate an insoluble barium-vanadium com- -plex, and separately recovering said insoluble complex and said solution.

6; The method of removing and recovering vanadium and aluminum salts fromsolutes comprising a preponderance of a mixture of alkali "metal chroma'tes with alkali metal aluminates I anda minorproportion of alkali metal vanadates,

which includes the steps of contacting a solution' comprising said solutes with a water insoluble inorganic'lead compound, adjusting the alkalinity of said solution to a pH within the range of 8-9 to'co-precipitate substantially all. -01 the vanadate ions and a minor proportion of the chromate ions as lead salts and substantially all of said alkali metal aluminates .as alumina hydrate, separating the co-precipitate from the remainder of said solution, con- ;ta'cting said co-precipitate with aqueous alkali metal hydroxide in stoichiometric excess of the amount required. to react with the aluminum andlead compounds of said co-precipitate to form a solution comprising alkali metal salts vanadium and aluminum salts from solutes comprising a preponderance of a mixture of alkali metal chromates with alkali metal aluminates and a minor proportion of alkali metal vanadates,

whichdncludes the steps of contacting a solution of said solutes with a source of lead ions, adjusting the alkalinity of said solution to a pH within the range of 8-9 to co-precipitate substantially all of the vanadate ions and a minor proportion of the chromate ions astheir leadv salts and substantially all of said alkali metal aluminates as alumina hydrate, separating the co-precipitate from the remainder of said 1'2 solution, contacting said co-precipitate with aqueousalkali metal hydroxide in stoichiometric excess of the amount required to react with the aluminum and lead compounds therein to form. a solution comprising alkali metal salts of the elementsof said co-precipitate, contacting said alkali-metal salt solution with a sourceoi sulfide ions to reduce the chromate ions and co-precipitate chromic hydroxide and lead sulsource of said lead ions.

fide, separating said. co-precip'itate from the remainder of the solution, contacting the remainder of the solution with a source of" barium ions to precipitate an insoluble complex containing substantially all of vanadium of said latter solution and substantially all of the barium'ions added thereto, separately recovering said insoluble barium-vanadium complex, recovering the remainder .of said latter solution as purified aqueous alkali metal aluminate, contacting said chromic hydroxide-lead sulfide co-precipitate with aqueous sulfuric acid to convert said chromic hydroxide to chromic sulfate and said lead sulfide to insoluble lead sulfate, recovering said insoluble lead sulfate, and recycling the same to the original solution of said solutes as said TOM s. PERRIN. ROBERT. G. BANNER.

, REFERENCES crrEn- The following references are of record in the file of this patent:

UNITED STATES PATENTS Number I Name. Date 620,935 Krebs Mar. 14, 1899 734,668 Suchy Nov, 10, 1903 868,807 Potter Oct. 22, 1907 1,784,950 'Udy Dec. 16, 1930 2,357,988 Van Wirt 1 Sept. 12, 194,4

OTHER REFERENCES Comey & Hahn-Dictionary of Chemical Solu bilities, Inorganic} 2nd Ed. pages 10 and 257. Publ. by the MacMillan Co NBW'YOlk, 1921'.

Analysis, 5thEd., page 136,Publ.-by D. Van Nostrand 00., New York, 1901.

Prescott & Johnson-Qualitative Chemical 1 

1. THE METHOD OF REMOVING AND RECOVERING VANADIUM AND ALUMINUM VALUES FROM AN ALKALINE SOLUTION HAVING A PH OF AT LEAST 10 COMPRISING THE SAME AS VANADATES AND ALUMINATES AND A PREPONDERANCE OF ALKALI METAL CHROMATES, WHICH INCLUDES THE STEPS OF CONTACTING SUCH SOLUTION WITH A LEAD COMPOUND WHICH PROVIDES A SOURCE OF LEAD IONS IN SAID SOLUTION, TO CO-PRECIPITATE SUBSTANTIALLY ALL OF THE VANDATE IONS AND AMINOR PROPORTION OF THE CHROMATE IONS AS THEIR LEAD SALTS, ADJUSTING THE ALKALINITY OF SAID SOLUTION TO A PH WITHIN THE RANGE OF 8-9 TO CONVERT SUBSTANTIALLY ALL OF SAID ALUMINUM VALUES TO ALUMINA HYDRATE, AND CO-PRECIPITATE SAID ALUMINA HYDRATE WITH SAID LEAD SALTS, AND SEPARATELY RECOVERING THE SUBSTANTIALLY VANADIUM AND ALUMINUM-FREE CHROMATE SOLUTION AND SAID CO-PRECIPITATE. 